Computational Exploration of Dirhodium Complex-Catalyzed Selective Intermolecular Amination of Tertiary vs. Benzylic C-H Bonds.

The mechanism and origins of site-selectivity of Rh(-tfpttl)-catalyzed C()-H bond aminations were studied using density functional theory (DFT) calculations. The synergistic combination of the dirhodium complex Rh(-tfpttl) with -butylphenol sulfamate TBPhsNH composes a pocket that can access both tertiary and benzylic C-H bonds. The nonactivated tertiary C-H bond was selectively aminated in the presence of an electronically activated benzylic C-H bond.